J. CHEM. RESEARCH (S), 1998 605
Some steryl ethers have been discovered in sediments2±4
and their origin is still unclear. The formation of cholesteryl
ethers under montmorillonite catalysis may have geo-
chemical implications,12 since montmorillonite clay is an
important class of clay mineral and is widespread in geologi-
cal samples.13±14 Thus we presume that steryl ethers in
sediments were formed from natural sterols and alcohols
catalysed by acidic clay minerals.
In conclusion, the present procedure on the solid surface
of montmorillonite K-10 provides a very convenient etheri®-
cation of cholesterol. The operational simplicity, mild con-
ditions, good yields and low cost make this procedure a
useful and attractive alternative to the currently available
methods.
23.82 (23), 37.12 (24), 28.01 (25), 22.55 (26 or 27), 22.81 (27 or 26),
156.33 (1'), 117.24 (2'), 129.31 (3'), 125.37 (4'), 129.31 (5'), 117.24
(6'); m/z 369 (100%).
2-Chlorophenyl cholesteryl ether 3k (Found: C, 79.63; H, 9.98;
Cl, 7.10; C33H49ClO requires C, 79.72; H, 9.93; Cl, 7.14%);
ꢀ
1
max/cm 1250, 1035; dH (80 MHz) 0.69 (3 H, s, 18-H3), 0.87 (6 H,
d, J 6.0, 26, 27-H6), 0.93 (3 H, d, J 6.0, 21-H3), 1.07 (3 H, s,
19-H3), 4.16 (1 H, m, W1/2 23.4, 3a-H), 5.42 (1 H, m, 6-H),
6.87±7.29 (4 H, m, Ar-H4); m/z 369 (100%).
4-Methylphenyl cholesteryl ether 3l (Found: C, 85.87; H, 10.94;
1
C
34H52O requires C, 85.65; H, 10.99%); ꢀmax/cm 1234, 1040; dH
(80 MHz) 0.69 (3 H, s, 18-H3), 0.87 (6 H, d, J 6.0, 26, 27-H6), 0.93
(3 H, d, J 6.1, 21-H3), 1.05 (3 H, s, 19-H3), 2.27 (3 H, s, 4'-CH3),
4.06 (1 H, m, W1/2 23.4, 3a-H), 5.38 (1 H, m, 6-H), 6.78 (2 H, d,
JAB 8.5, 2',6'-H2), 7.05 (2 H, d, JAB 8.5, 3',5'-H2); m/z 476 (M ,
6%), 369 (100).
3-Methylphenyl cholesteryl ether 3m (Found: C, 85.95; H, 10.83;
1
C34H52O requires C, 85.65; H, 10.99%); ꢀmax/cm 1255, 1055; dH
Experimental
(80 MHz) 0.69 (3 H, s, 18-H3), 0.87 (6 H, d, J 6.0, 26, 27-H6), 0.93
(3 H, d, J 6.0, 21-H3), 1.06 (3 H, s, 19-H3), 2.48 (3 H, s, 3'-CH3),
4.10 (1 H, m, W1/2 23.1 Hz, 3a-H), 5.38 (1 H, m, 6-H), 6.73 (3 H,
Melting points were uncorrected. Elemental analyses were
determined on a Hearu CHN-Rapid instrument. Infrared spectra
were recorded on Perkin-Elmer 983G and FTS-40 IR spectrometers.
1H and 13C NMR spectra were measured on Bruker AC-80, Bruker
AM-400 and Varian INOVA-500 spectrometers, using CDCl3 as
solvent and tetramethylsilane as internal reference. J values are in
Hz. Mass spectra were obtained on a VG-7070E spectrometer, elec-
tion impact, 70 eV.
Typical Procedure.ÐA mixture of methanol (1a, 320 mg,
10.0 mmol), chloroform (10 ml), cholesterol (2, 386 mg, 1.0 mmol)
and montmorillonite K-10 (0.8 g, from Aldrich, activated at 120 8C
overnight prior to use) was stirred at 55±60 8C on an oil bath for
13 h. After completion, the catalyst was removed by ®ltration and
washed with diethyl ether. Evaporation of the solvent yielded crude
cholesteryl methyl ether. The crude product was puri®ed by short
column chromatography on silica gel to give cholesteryl methyl
ether (3a, 275 mg, 69%).
m, 2',4',6'-H3), 7.14 (1 H, t, J 8.4, 5'-H); m/z 476 (M , 8%), 369
(100).
2-Methylphenyl cholesteryl ether 3n (Found: C, 85.90; H, 10.78;
1
C34H52O requires C, 85.65; H, 10.99%); ꢀmax/cm 1235, 1040; dH
(80 MHz) 0.69 (3 H, s, 18-H3) 0.86 (6 H, d, J 6.0, 26, 27-H6), 0.93
(3 H, d, J 6.0, 21-H3), 1.07 (3 H, s, 19-H3), 2.21 (3 H, s, 2'-CH3),
4.13 (1 H, m, W1/2 23.2, 3a-H), 5.41 (1 H, m, 6-H), 6.81±7.19 (4 H,
m, Ar-H4); m/z 476 (M , 2%), 369 (100).
4-Methoxyphenyl cholesteryl ether 3o (Found: C, 82.61; H, 10.47;
max/cm
1
C34H52O2 requires C, 82.87; H, 10.64%);
ꢀ
1040; dH
(80 MHz) 0.69 (3 H, s, 18-H3), 0.86 (6 H, d, J 6.0, 26, 27-H6), 0.93
(3 H, d, J 6.0, 21-H3), 1.05 (3 H, s, 19-H3), 3.76 (3 H, s, 4'-OCH3),
3.95 (1 H, m, W1/2 23.4, 3a-H), 5.35 (1 H, m, 6-H), 6.82 (4 H, s,
Ar-H4); dC (100 MHz, DEPT) 39.51 (1), 31.93 (2), 78.21 (3), 39.76
(4), 140.45 (5), 122.14 (6), 31.93 (7), 31.88 (8), 50.19 (9), 36.62 (10),
21.07 (11), 28.22 (12), 42.31 (13), 56.75 (14), 24.48 (15), 38.65 (16),
56.15 (17), 11.85 (18), 19.41 (19), 35.77 (20), 18.71 (21), 36.18 (22),
23.82 (23), 37.18 (24), 28.00 (25), 22.55 (26), 22.81 (27), 153.70 (1'),
117.52 (2'), 114.58 (3'), 151.66 (4'), 114.58 (5'), 117.52 (6'), 55.65
n-Butyl cholesteryl ether 3b, dH (500 MHz) 0.674 (3 H, s, 18-H3),
0.862, 0.866 (6 H, 2d, J 6.5, 26, 27-H6), 0.912 (3 H, d, J 6.0, 21-H3),
0.917 (3 H, t, J 7.3, 4'-H3), 0.998 (3 H, s, 19-H3), 3.126 (1 H, m,
W1/2 22.5, 3a-H), 3.458 (2 H, t, J 7.0, 1'-H2), 5.344 (1 H, m, 6-H).
Decyl cholesteryl ether 3c (Found: C, 84.71; H, 12.51; C37H66
O
(-OCH3); m/z 492 (M , 13%), 369 (100).
requires C, 84.43; H, 12.62%); dH (400 MHz) 0.674 (3 H, s, 18-H3),
0.862, 0.866 (6 H, 2d, J 6.6, 26, 27-H6), 0.913 (3 H, d, J 6.5, 21-H3),
0.999 (3 H, s, 19-H3), 3.125 (1 H, m, W1/2 24.8, 3a-H), 3.446 (2 H,
t, J 6.7, 1'-H2), 5.345 (1 H, m, 6-H).
Benzyl cholesteryl ether 3d, dH (500 MHz) 0.675 (3 H, s, 18-H3),
0.861, 0.866 (6 H, 2d, J 6.5, 26, 27-H6), 0.912 (3 H, d, J 6.0, 21-H3),
1.013 (3 H, s, 19-H3), 3.281 (1 H, m, W1/2 23.0, 3a-H), 4.557, 4.570
(2 H, 2d, JAB 12.0, 1'-H2), 5.349 (1 H, m, 6-H), 7.347 (5 H, s,
Ph-H5).
This project was supported by NSFC (2957039), Natural
Science Foundation of Hebei Province (297065) and the
Science and Technology Commission of Hebei Province.
Received, 23rd April 1998; Accepted, 1st June 1998
Paper E/8/03050B
2-Butyl cholesteryl ether 3e, dH (500 MHz) 0.674 (3 H, s, 18-H3),
0.862, 0.867 (6 H, 2d, J 6.0, 26, 27-H6), 0.896 [1.5 H, t, J 7.5,
(R)-3'- or (S)-3'-Me], 0.903 [1.5 H, t, J 7.5, (S)-3'- or (R)-3'-Me],
0.913 (3 H, d, J 6.0, 21-H3), 1.002 (3 H, s, 19-H3), 1.115 [1.5 H, d,
J 6.3, (R)-1'- or (S)-1'-Me], 1.115 [1.5 H, d, J 6.3, (S)-1'- or (R)-1'-
Me], 3.192 (1 H, m, W1/2 22.4, 3), 3.425 (1 H, m, 1'-H), 5.342 (1 H,
m, 6-H).
References
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3-Pentyl cholesteryl ether 3f (Found: C, 84.09; H, 12.45; C32H56
O
1
requires C, 84.14; H, 12.36%); ꢀmax/cm 1084; dH (500 MHz) 0.675
(3 H, s, 18-H3), 0.862, 0.867 (6 H, 2d, J 6.5, 26, 27-H6), 0.919 (3 H,
d, J 6.5, 21-H3), 0.893, 0.902 (6 H, 2t, J 7.0, 3'-H3 and 1'-CH2CH3),
1.004 (3 H, s, 19-H3), 3.177 (2 H, m, W1/2 25.3, 3a-H and 1'-H),
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4 J. J. Boon and J. W. de Leeuw, Mar. Chem., 1979, 7, 117.
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6 B. Borgstrom, Proc. Soc. Exp. Biol. Med., 1968, 127, 1120.
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5.337 (1 H, m, 6-H); m/z 456 (M , 11%), 369 (38), 57 (100).
1
Phenyl cholesteryl ether 3i, ꢀmax/cm 1231, 1040; dH (80 MHz)
0.69 (3 H, s, 18-H3), 0.87 (6 H, d, J 6.0, 26, 27-H6), 0.93 (3 H, d,
J 6.1, 21-H3), 1.06 (3 H, s, 19-H3), 4.06 (1 H, m, W1/2 26.7, 3a-H),
5.41 (1 H, m, 6-H), 6.83±7.18 (5 H, m, Ar-H5); m/z 462 (M , 1%),
369 (100).
4-Chlorophenyl cholesteryl ether 3j (Found: C, 79.42; H, 10.15;
Cl, 7.15; C33H49ClO requires C, 79.72; H, 9.93; Cl, 7.13%);
1
ꢀ
max/cm 1237, 1038; dH (80 MHz) 0.69 (3 H, s, 18-H3), 0.86 (6 H,
d, J 6.0, 26, 27-H6), 0.91 (3 H, d, J 6.4, 21-H3), 1.05 (3 H, s, 19-
H3), 4.06 (1 H, m, W1/2 21.8, 3a-H), 5.38 (1 H, m, 6-H), 6.80 (2 H,
d, JAB 9.0, 2',6'-H2), 7.19 (2 H, d, JAB 9.0, 3',5'-H2); dC (100 MHz,
DEPT, number of carbon) 39.51 (1), 28.22 (2), 77.52 (3), 39.75 (4),
140.10 (5), 122.48 (6), 31.93 (7), 31.88 (8), 50.19 (9), 36.81 (10),
21.07 (11), 28.13 (12), 42.32 (13), 56.75 (14), 24.28 (15), 38.55 (16),
56.16 (17), 11.86 (18), 19.40 (19), 35.77 (20), 18.72 (21), 36.18 (22),
11 T. Akiyama, H. Hirofuji and S. Ozaki, Bull. Chem. Soc. Jpn.,
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12 A. S. Mackenzie, S. C. Brassell, G. Eglinton and J. R. Maxwell,
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